Polyethylene composition having high swell ratio

ABSTRACT

Polyethylene composition with improved swell ratio and mechanical properties, particularly suited for preparing blow-moulded articles, said composition having the following features: 
     1) density from 0.945 to less than 0.952 g/cm 3 ;
 
2) ratio MIF/MIP from 15 to 30;
 
3) Shear-Induced Crystallization Index SIC from 2.5 to 5.5.

FIELD OF THE INVENTION

The present invention provides a polyethylene composition suitable for preparing various kinds of formed articles. In particular, due to its enhanced processability, high die-swell with high-quality surface and dimension stability of final article, environmental stress cracking resistance (FNCT) and impact resistance, the present composition is suitable for making extrusion blow-moulded hollow articles, such as drums, containers and gasoline storage tanks.

The present invention also relates to a multi-stage polymerization process for preparing the said polyethylene composition.

BACKGROUND OF THE INVENTION

An additional and important advantage of the polyethylene composition of the present invention is that it can be melt-processed at unusually high shear rate values, which mean high processing speeds and/or reduced melt-processing temperatures, without encountering flow-instabilities which generally produce unacceptable defects in the formed articles (e.g. shark skin or melt-fracture), even in the absence of processing aids.

Moreover, the fast crystallization kinetics of the present composition, which provides a critical contribution to its superior process-ability, also provides an unusually reduced shrinkage of the formed articles, thus allowing achieving a remarkable dimensional stability. Thus the composition of the present invention provides an unmatched balance of mechanical properties and process-ability with respect to the known polyethylene compositions for the same use, as disclosed in particular in U.S. Pat. No. 6,201,078.

In fact, the polymers disclosed in U.S. Pat. No. 6,201,078 achieve a relatively low balance of swell ratio and environmental stress cracking resistance, as shown in the examples.

The problem of achieving a high impact resistance, reducing the flow-instabilities and improving the dimensional stability (lowering shrinkage) is not mentioned in such document.

SUMMARY OF THE INVENTION

Thus the present invention provides a polyethylene composition having the following features:

-   -   1) density from 0.945 to less than 0.952 g/cm³, preferably from         0.948 to 0.951 g/cm³, determined according to ISO 1183 at 23°         C.;     -   2) ratio MIF/MIP from 15 to 30, in particular from 17 to 29,         where MIF is the melt flow index at 190° C. with a load of 21.60         kg, and MIP is the melt flow index at 190° C. with a load of 5         kg, both determined according to ISO 1133;     -   3) SIC Index from 2.5 to 5.5, preferably from 2.5 to 4.5, more         preferably from 3.2 to 3.9;     -   wherein the SIC Index is the Shear-Induced Crystallization         Index, determined according to the following relation:

SIC Index=(t _(onset,SIC)@1000×t _(onset,quiescent))/(HLMI)

-   -   where t_(onset,SIC)@1000 is measured in seconds and is the time         required for a crystallization onset under shear rate of 1000         s⁻¹, the t_(onset, quiescent) is measured in seconds and is the         crystallization onset time at temperature of 125° C. under no         shear, determined in isothermal mode by differential scanning         calorimetry (DSC); HLMI is the melt flow index determined at         190° C. with a load of 21.6 kg, according to ISO 1133.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the present disclosure will become better understood with reference to the following description and appended claims, and accompanying drawing FIGURE where:

The drawing is an illustrative embodiment of a simplified process-flow diagram of two serially connected gas-phase reactors suitable for use in accordance with various embodiments of ethylene polymerization processes disclosed herein to produce various embodiments of the polyethylene compositions disclosed herein.

It should be understood that the various embodiments are not limited to the arrangements and instrumentality shown in the drawing FIGURE.

DETAILED DESCRIPTION OF THE INVENTION

The expression “polyethylene composition” is intended to embrace, as alternatives, both a single ethylene polymer and an ethylene polymer composition, in particular a composition of two or more ethylene polymer components, preferably with different molecular weights, such composition being also called “bimodal” or “multimodal” polymer in the relevant art. Typically the polyethylene composition of the present invention consists of or comprises one or more ethylene copolymers.

All the features herein defined, comprising the previously defined features 1) to 3), are referred to the said ethylene polymer or ethylene polymer composition. The addition of other components, like the additives normally employed in the art, can modify one or more of said features.

The ratio MIF/MIP provides a rheological measure of molecular weight distribution.

Another measure of the molecular weight distribution is provided by the ratio Mw/Mn, where Mw is the weight average molar mass and Mn is the number average molar mass, both measured by GPC (Gel Permeation Chromatography), as explained in the examples. Preferred Mw/Mn values for the polyethylene composition of the present invention range from 20 to 30.

Moreover the polyethylene composition of the present invention has preferably at least one of the following additional features.

-   -   Mw equal to or greater than 250000 g/mol, more preferably equal         to or greater than 280000 g/mol, in particular equal to or         greater than 300000 g/mol;     -   Long Chain Branching index (LCB) determined as described in the         examples, equal to or greater than 0.70, more preferably equal         to or greater than 0.72, in particular equal to or greater than         0.80;     -   MIP: 0.05-0.5 g/10 min.;     -   MIF: 1-15 g/10 min;     -   Comonomer content equal to or less than 1% by weight, in         particular from 0.05 to 1% by weight, with respect to the total         weight of the composition.

The comonomer or comonomers present in the ethylene copolymers are generally selected from olefins having formula CH₂═CHR wherein R is an alkyl radical, linear or branched, having from 1 to 10 carbon atoms.

Specific examples are propylene, butene-1, pentene-1,4-methylpentene-1, hexene-1, octene-1 and decene-1. A particularly preferred comonomer is hexene-1.

In particular, in a preferred embodiment, the present composition comprises:

-   A) 30-50% by weight of an ethylene homopolymer or copolymer (the     homopolymer being preferred) with density equal to or greater than     0.960 g/cm³ and melt flow index MIE at 190° C. with a load of 2.16     kg, according to ISO 1133, of 10-35 g/10 min.; -   B) 50-70% by weight of an ethylene copolymer having a MIE value     lower than the MIE value of A), preferably lower than 0.5 g/10 min.

The above percent amounts are given with respect to the total weight of A)+B).

The amount of comonomer in B) is preferably from 0.1 to 2% by weight, with respect to the total weight of B).

As previously said, the present polyethylene composition can be advantageously used in the preparation of extrusion blow-moulded hollow articles, in particular large blow moulded articles such as open-top-drums (OTD) or industrial-bulk-containers (IBC), thanks to its valuable mechanical properties.

In fact it is preferably characterized by the following properties.

-   -   FNCT equal to or greater than 10 hours, more preferably equal to         or greater than 100 hours, in particular equal to or greater         than 150 hours, measured at 4 MPa, 80° C.;     -   Notch Tensile Impact (−30° C.) equal to or greater than 100         kJ/m²;     -   Critical shear-rate for shark skin (190° C.) equal to or greater         than 250 s⁻¹;     -   Die swell-ratio equal to or greater than 150%;     -   Shrinkage at 1500 s⁻¹ (190° C.) equal to or smaller than 17%.

The details of the test methods are given in the examples.

In particular the shark skin test (critical shear rate for shark skin) provides an indication of the shear rate at which flow-instabilities start due to pressure oscillations, thus of the melt processing conditions, and consequently of the extrusion throughput, at which irregularities on the surface of the extruded piece become visible. Such irregularities strongly reduce surface gloss and smoothness, thus lowering the quality of the extruded article to an unacceptable level.

As previously mentioned, the polyethylene composition of the present invention can be melt-processed at surprisingly high values of shear rate, still without undergoing pressure oscillations and flow-instabilities.

While no necessary limitation is known to exist in principle on the kind of polymerization processes and catalysts to be used, it has been found that the polyethylene composition of the present invention can be prepared by a gas phase polymerization process in the presence of a Ziegler-Natta catalyst.

A Ziegler-Natta catalyst comprises the product of the reaction of an organometallic compound of group 1, 2 or 13 of the Periodic Table of elements with a transition metal compound of groups 4 to 10 of the Periodic Table of Elements (new notation). In particular, the transition metal compound can be selected among compounds of Ti, V, Zr, Cr and Hf and is preferably supported on MgCl₂.

Particularly preferred catalysts comprise the product of the reaction of said organometallic compound of group 1, 2 or 13 of the Periodic Table of elements, with a solid catalyst component comprising a Ti compound and an electron donor compound (ED) supported on MgCl₂.

Preferred organometallic compounds are the organo-Al compounds.

Thus in a preferred embodiment, the polyethylene composition of the present invention is obtainable by using a Ziegler-Natta polymerization catalyst, more preferably a Ziegler-Natta catalyst supported on MgCl₂, even more preferably a Ziegler-Natta catalyst comprising the product of reaction of:

-   a) a solid catalyst component comprising a Ti compound and an     electron donor compound ED supported on MgCl₂; -   b) an organo-Al compound; and optionally -   c) an external electron donor compound ED_(ext).

Preferably in component a) the ED/Ti molar ratio ranges from 1.5 to 3.5 and the Mg/Ti molar ratio is higher than 5.5, in particular from 6 to 80.

Among suitable titanium compounds are the tetrahalides or the compounds of formula TiX_(n)(OR¹)_(4-n), where 0≦n≦3, X is halogen, preferably chlorine, and R¹ is C₁-C₁₀ hydrocarbon group. The titanium tetrachloride is the preferred compound.

The ED compound is generally selected from alcohol, ketones, amines, amides, nitriles, alkoxysilanes, aliphatic ethers, and esters of aliphatic carboxylic acids.

Preferably the ED compound is selected among, amides, esters and alkoxysilanes.

Excellent results have been obtained with the use of esters which are thus particularly preferred as ED compound. Specific examples of esters are the alkyl esters of C1-C20 aliphatic carboxylic acids and in particular C1-C8 alkyl esters of aliphatic mono carboxylic acids such as ethylacetate, methyl formiate, ethylformiate, methylacetate, propylacetate, propylacetate, n-butylacetate, i-butylacetate. Moreover, are also preferred the aliphatic ethers and particularly the C2-C20 aliphatic ethers, such as tetrahydrofurane (THF) or dioxane.

In the said solid catalyst component the MgCl₂ is the basic support, even if minor amount of additional carriers can be used. The MgCl₂ can be used as such or obtained from Mg compounds used as precursors that can be transformed into MgCl₂ by the reaction with halogenating compounds. Particularly preferred is the use of MgCl₂ in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts. Patents U.S. Pat. No. 4,298,718 and U.S. Pat. No. 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the magnesium dihalides in active form used as support or co-support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the ASTM-card reference of the spectrum of the non-active halide is diminished in intensity and broadened. In the X-ray spectra of preferred magnesium dihalides in active form said most intense line is diminished in intensity and replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the most intense line. Particularly suitable for the preparation of the polyethylene composition of the present invention are the catalysts wherein the solid catalyst component a) is obtained by first contacting the titanium compound with the MgCl₂, or a precursor Mg compound, optionally in the presence of an inert medium, thus preparing an intermediate product a′) containing a titanium compound supported on MgCl₂, which intermediate product a′) is then contacted with the ED compound which is added to the reaction mixture alone or in a mixture with other compounds in which it represents the main component, optionally in the presence of an inert medium.

With the term “main component” we intend that the said ED compound must be the main component in terms of molar amount, with respect to the other possible compounds excluded inert solvents or diluents used to handle the contact mixture. The ED treated product can then be subject to washings with the proper solvents in order to recover the final product. If needed, the treatment with the ED compound desired can be repeated one or more times.

As previously mentioned, a precursor of MgCl₂ can be used as starting essential Mg compound. This can be selected for example among Mg compound of formula MgR′₂ where the R′ groups can be independently C1-C20 hydrocarbon groups optionally substituted, OR groups, OCOR groups, chlorine, in which R is a C1-C20 hydrocarbon groups optionally substituted, with the obvious proviso that the R′ groups are not simultaneously chlorine. Also suitable as precursors are the Lewis adducts between MgCl₂ and suitable Lewis bases. A particular and preferred class being constituted by the MgCl₂ (R″OH)_(m) adducts in which R″ groups are C1-C20 hydrocarbon groups, preferably C1-C10 alkyl groups, and m is from 0.1 to 6, preferably from 0.5 to 3 and more preferably from 0.5 to 2. Adducts of this type can generally be obtained by mixing alcohol and MgCl₂ in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130° C.). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Representative methods for the preparation of these spherical adducts are reported for example in U.S. Pat. No. 4,469,648, U.S. Pat. No. 4,399,054, and WO98/44009. Another useable method for the spherulization is the spray cooling described for example in U.S. Pat. Nos. 5,100,849 and 4,829,034.

Particularly interesting are the MgCl₂.(EtOH)_(m) adducts in which m is from 0.15 to 1.7 obtained subjecting the adducts with a higher alcohol content to a thermal dealcoholation process carried out in nitrogen flow at temperatures comprised between 50 and 150° C. until the alcohol content is reduced to the above value. A process of this type is described in EP 395083.

The dealcoholation can also be carried out chemically by contacting the adduct with compounds capable to react with the alcohol groups.

Generally these dealcoholated adducts are also characterized by a porosity (measured by mercury method) due to pores with radius up to 0.1 μm ranging from 0.15 to 2.5 cm³/g preferably from 0.25 to 1.5 cm³/g.

It is preferred that the dealcoholation reaction is carried out simultaneously with the step of reaction involving the use of a titanium compound. Accordingly, these adducts are reacted with the TiX_(n)(OR¹)_(4-n) compound (or possibly mixtures thereof) mentioned above which is preferably titanium tetrachloride. The reaction with the Ti compound can be carried out by suspending the adduct in TiCl₄ (generally cold). The mixture is heated up to temperatures ranging from 80-130° C. and kept at this temperature for 0.5-2 hours. The treatment with the titanium compound can be carried out one or more times. Preferably it is repeated twice. It can also be carried out in the presence of an electron donor compound as those mentioned above. At the end of the process the solid is recovered by separation of the suspension via the conventional methods (such as settling and removing of the liquid, filtration, centrifugation) and can be subject to washings with solvents. Although the washings are typically carried out with inert hydrocarbon liquids, it is also possible to use more polar solvents (having for example a higher dielectric constant) such as halogenated hydrocarbons.

As mentioned above, the intermediate product is then brought into contact with the ED compound under conditions able to fix on the solid an effective amount of donor. Due to the high versatility of this method, the amount of donor used can widely vary. As an example, it can be used in molar ratio with respect to the Ti content in the intermediate product ranging from 0.5 to 20 and preferably from 1 to 10. Although not strictly required the contact is typically carried out in a liquid medium such as a liquid hydrocarbon. The temperature at which the contact takes place can vary depending on the nature of the reagents. Generally it is comprised in the range from −10° to 150° C. and preferably from 0° to 120° C. It is plane that temperatures causing the decomposition or degradation of any specific reagents should be avoided even if they fall within the generally suitable range. Also the time of the treatment can vary in dependence of other conditions such as nature of the reagents, temperature, concentration etc. As a general indication this contact step can last from 10 minutes to 10 hours more frequently from 0.5 to 5 hours. If desired, in order to further increase the final donor content, this step can be repeated one or more times. At the end of this step the solid is recovered by separation of the suspension via the conventional methods (such as settling and removing of the liquid, filtration, centrifugation) and can be subject to washings with solvents. Although the washings are typically carried out with inert hydrocarbon liquids, it is also possible to use more polar solvents (having for example a higher dielectric constant) such as halogenated or oxygenated hydrocarbons.

As previously mentioned, the said solid catalyst component is converted into catalysts for the polymerization of olefins by reacting it, according to known methods, with an organometallic compound of group 1, 2 or 13 of the Periodic Table of elements, in particular with an Al-alkyl compound.

The alkyl-Al compound is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt₂Cl and Al₂Et₃Cl₃ optionally in mixture with said trialkyl aluminum compounds.

The external electron donor compound ED_(ext) optionally used to prepare the said Ziegler-Natta catalysts can be equal to or different from the ED used in the solid catalyst component a). Preferably it is selected from the group consisting of ethers, esters, amines, ketones, nitriles, silanes and their mixtures. In particular it can advantageously be selected from the C2-C20 aliphatic ethers and in particulars cyclic ethers preferably having 3-5 carbon atoms such as tetrahydrofurane and dioxane.

Specific examples of the above described Ziegler-Natta catalysts and of methods for their preparation are provided in WO2004106388. However, the therein described prepolymerization of the solid catalyst component containing the Ti compound and the electron donor compound ED (solid catalyst component a)) is not comprised in the preferred embodiments according to the present invention.

In particular, the polyethylene composition of the present invention is obtainable by a process wherein all the polymerization steps are carried out in the presence of the said catalyst.

In fact it has been found that by using the above described polymerization catalyst, the polyethylene composition of the present invention can be prepared in a process comprising the following steps, in any mutual order:

-   a) polymerizing ethylene, optionally together with one or more     comonomers, in a gas-phase reactor in the presence of hydrogen; -   b) copolymerizing ethylene with one or more comonomers in another     gas-phase reactor in the presence of an amount of hydrogen less than     step a);     where in at least one of said gas-phase reactors the growing polymer     particles flow upward through a first polymerization zone (riser)     under fast fluidization or transport conditions, leave said riser     and enter a second polymerization zone (downcomer) through which     they flow downward under the action of gravity, leave said downcomer     and are reintroduced into the riser, thus establishing a circulation     of polymer between said two polymerization zones. In the first     polymerization zone (riser), fast fluidization conditions are     established by feeding a gas mixture comprising one or more olefins     (ethylene and comonomers) at a velocity higher than the transport     velocity of the polymer particles. The velocity of said gas mixture     is preferably comprised between 0.5 and 15 m/s, more preferably     between 0.8 and 5 m/s. The terms “transport velocity” and “fast     fluidization conditions” are well known in the art; for a definition     thereof, see, for example, “D. Geldart, Gas Fluidisation Technology,     page 155 et seq., J. Wiley & Sons Ltd., 1986”.

In the second polymerization zone (downcomer), the polymer particles flow under the action of gravity in a densified form, so that high values of density of the solid are reached (mass of polymer per volume of reactor), which approach the bulk density of the polymer.

In other words, the polymer flows vertically down through the downcomer in a plug flow (packed flow mode), so that only small quantities of gas are entrained between the polymer particles.

Such process allows to obtain from step a) an ethylene polymer with a molecular weight lower than the ethylene copolymer obtained from step b).

Preferably, the polymerization of ethylene to produce a relatively low molecular weight ethylene polymer (step a) is performed upstream the copolymerization of ethylene with a comonomer to produce a relatively high molecular weight ethylene copolymer (step b). To this aim, in step a) a gaseous mixture comprising ethylene, hydrogen and an inert gas is fed to a first gas-phase reactor, preferably a gas-phase fluidized bed reactor. The polymerization is carried out in the presence of the previously described Ziegler-Natta catalyst. Preferably, no comonomer is fed to said first gas phase reactor and a highly crystalline ethylene homopolymer is obtained in step a). However, a minimal amount of comonomer may be fed with the proviso that the degree of copolymerization in step a) is limited so that the density of the ethylene polymer obtained in step a) is not less than 0.960 g/cm³.

Hydrogen is fed in an amount depending on the specific catalyst used and, in any case, suitable to obtain in step a) an ethylene polymer with a melt flow index MIE from 10 to 35 g/10 min. In order to obtain the above MIE range, in step a) the hydrogen/ethylene molar ratio is indicatively from 0.5 to 2, the amount of ethylene monomer being from 5 to 50% by volume, preferably from 5 to 30% by volume, based on the total volume of gas present in the polymerization reactor. The remaining portion of the feeding mixture is represented by inert gases and one or more comonomers, if any. Inert gases which are necessary to dissipate the heat generated by the polymerization reaction are conveniently selected from nitrogen or saturated hydrocarbons, the most preferred being propane.

The operating temperature in the reactor of step a) is selected between 50 and 120° C., preferably between 65 and 100° C., while the operating pressure is between 0.5 and 10 MPa, preferably between 2.0 and 3.5 MPa.

In a preferred embodiment, the ethylene polymer obtained in step a) represents from 30 to 50% by weight of the total ethylene polymer produced in the overall process, i.e. in the first and second serially connected reactors.

The ethylene polymer coming from step a) and the entrained gas are then passed through a solid/gas separation step, in order to prevent the gaseous mixture coming from the first polymerization reactor from entering the reactor of step b) (second gas-phase polymerization reactor). Said gaseous mixture can be recycled back to the first polymerization reactor, while the separated ethylene polymer is fed to the reactor of step b). A suitable point of feeding of the polymer into the second reactor is on the connecting part between the downcomer and the riser, wherein the solid concentration is particularly low, so that the flow conditions are not negatively affected.

The operating temperature in step b) is in the range of 65 to 95° C., and the pressure is in the range of 1.5 to 4.0 MPa. The second gas-phase reactor is aimed to produce a relatively high molecular weight ethylene copolymer by copolymerizing ethylene with one or more comonomers. Furthermore, in order to broaden the molecular weight distribution of the final ethylene polymer, the reactor of step b) can be conveniently operated by establishing different conditions of monomers and hydrogen concentration within the riser and the downcomer.

To this purpose, in step b) the gas mixture entraining the polymer particles and coming from the riser can be partially or totally prevented from entering the downcomer, so to obtain two different gas composition zones. This can be achieved by feeding a gas and/or a liquid mixture into the downcomer through a line placed at a suitable point of the downcomer, preferably in the upper part thereof. Said gas and/or liquid mixture should have a suitable composition, different from that of the gas mixture present in the riser. The flow of said gas and/or liquid mixture can be regulated so that an upward flow of gas counter-current to the flow of the polymer particles is generated, particularly at the top thereof, acting as a barrier to the gas mixture entrained among the polymer particles coming from the riser. In particular, it is advantageous to feed a mixture with low content of hydrogen in order to produce the higher molecular weight polymer fraction in the downcomer. One or more comonomers can be fed to the downcomer of step b), optionally together with ethylene, propane or other inert gases.

The hydrogen/ethylene molar ratio in the downcomer of step b) is comprised between 0.005 and 0.2, the ethylene concentration being comprised from 1 to 20%, preferably 3-10%, by volume, the comonomer concentration being comprised from 0.2 to 1% by volume, based on the total volume of gas present in said downcomer. The rest is propane or similar inert gases. Since a very low molar concentration of hydrogen is present in the downcomer, by carrying out the process of the present invention is possible to bond a relatively high amount of comonomer to the high molecular weight polyethylene fraction.

The polymer particles coming from the downcomer are reintroduced in the riser of step b).

Since the polymer particles keep reacting and no more comonomer is fed to the riser, the concentration of said comonomer drops to a range of 0.1 to 0.5% by volume, based on the total volume of gas present in said riser. In practice, the comonomer content is controlled in order to obtain the desired density of the final polyethylene. In the riser of step b) the hydrogen/ethylene molar ratio is in the range of 0.05 to 0.3, the ethylene concentration being comprised between 5 and 15% by volume based on the total volume of gas present in said riser. The rest is propane or other inert gases.

More details on the above described polymerization process are provided in WO9412568.

EXAMPLES

The following examples are given to illustrate, without limiting, the present invention.

Unless differently stated, the following test methods are used to determine the properties reported in the detailed description and in the examples.

Density

-   -   Determined according to ISO 1183 at 23° C.

Molecular Weight Distribution Determination

-   -   The determination of the molar mass distributions and the means         Mn, Mw and Mw/Mn derived therefrom was carried out by         high-temperature gel permeation chromatography using a method         described in ISO 16014-1, -2, -4, issues of 2003. The specifics         according to the mentioned ISO standards are as follows: Solvent         1,2,4-trichlorobenzene (TCB), temperature of apparatus and         solutions 135° C. and as concentration detector a PolymerChar         (Valencia, Paterna 46980, Spain) IR-4 infrared detector, capable         for use with TCB. A WATERS Alliance 2000 equipped with the         following pre-column SHODEX UT-G and separation columns SHODEX         UT 806 M (3×) and SHODEX UT 807 (Showa Denko Europe GmbH,         Konrad-Zuse-Platz 4, 81829 Muenchen, Germany) connected in         series was used. The solvent was vacuum distilled under Nitrogen         and was stabilized with 0.025% by weight of         2,6-di-tert-butyl-4-methylphenol. The flowrate used was 1         ml/min, the injection was 500 μl and polymer concentration was         in the range of 0.01%<conc.<0.05% w/w. The molecular weight         calibration was established by using monodisperse polystyrene         (PS) standards from Polymer Laboratories (now Agilent         Technologies, Herrenberger Str. 130, 71034 Boeblingen, Germany))         in the range from 580 g/mol up to 11600000 g/mol and         additionally with Hexadecane. The calibration curve was then         adapted to Polyethylene (PE) by means of the Universal         Calibration method (Benoit H., Rempp P. and Grubisic Z., & in J.         Polymer Sci., Phys. Ed., 5, 753(1967)). The Mark-Houwing         parameters used herefore were for PS: k_(PS)=0.000121 dl/g,         α_(PS)=0.706 and for PE k_(PE)=0.000406 dl/g, α_(PE)=0.725,         valid in TCB at 135° C. Data recording, calibration and         calculation was carried out using NTGPC_Control_V6.02.03 and         NTGPC_V6.4.24 (hs GmbH, Hauptstraβe 36, D-55437         Ober-Hilbersheim, Germany) respectively.

Shear-Induced Crystallization Test

-   -   This method is utilized to determine the onset time of         shear-induced crystallization (SIC) of the polymer,         t_(onset,SIC). Samples are melt-pressed at 210° C., 4 min, under         200 bar in a lab press to 1 mm thick-plaques. Disc specimens are         cut-out with a diameter of 25 mm. The samples are inserted in         the plate-plate oscillatory-shear rheometer. A Physica MCR 301         rotational rheometer from AntonPaar is used.     -   The sample is then molten inside the test-geometry at 190° C.         for 4 min, cooled down with ˜10K/min to the test temperature,         T=125° C., and annealed for 5 min. Consequently, steady-shear         under constant shear rate is applied and the shear viscosity is         monitored as a function of time. The experiment is repeated         applying each time a different shear-rate ranging from 0.05 to         0.5 s⁻¹. The onset time for SIC, t_(onset,SIC), is taken at the         point where the viscosity has increased at 50% of its         steady-state value η@125° C. The steady-state value is the         average of the steady-shear melt viscosity measured at the         specific temperature.     -   The plot of log t_(onset,SIC) vs. log shear-rate provides a         linear function (of type y=Ax+B) which is extrapolated to a         shear rate of 1000 s⁻¹ (process-relevant) to determine the value         of t_(onset,SIC)@1000.     -   The SIC Index is then calculated according to the following         relation:

SIC Index=(t _(onset,SIC)*1000×t _(onset,quiescent))/(HLMI)

-   -   The t_(onset, quiescent) (in sec) is the crystallization onset         at temperature of 125° C. under quiescent conditions, i.e. no         shear, measured in isothermal mode in a         differential-scanning-calorimetry apparatus, DSC, as hereinafter         explained.     -   HLMI is the melt flow index (g/10 min) measured at T=190° C.         with 21.6 kg load, according to ISO 1133.     -   The same protocol is described in the following documents.

-   I. Vittorias, Correlation among structure, processing and product     properties, Würzburger Tage 2010, Wolfgang Kunze TA Instruments,     Germany.

-   Wo D L, Tanner R I (2010), The impact of blue organic and inorganic     pigments on the crystallization and rheological properties of     isotactic polypropylene, Rheol. Acta 49, 75.

-   Derakhshandeh M., Hatzikiriakos S. G., Flow-induced crystallization     of high-density polyethylene: the effects of shear and uniaxial     extension, Rheol. Acta, 51, 315-327, 2012.

Isothermal DSC

-   -   The t_(onset,quiescent), the onset time when no deformation is         applied at 125° C., is determined by the iso-DSC (isothermal         Differential Scanning calorimetry) method. It is measured at         125° C. in a TA Instruments Q2000 DSC apparatus. The         determination of the t_(onset,quiescent) is performed utilizing         the commercially available software TA Universal Analysis 2000.         The sample preparation and set-up follows the DIN EN ISO         11357-1:2009 and ISO 11357-3:1999.

Melt Flow Index

-   -   Determined according to ISO 1133 at 190° C. with the specified         load.

Long Chain Branching Index (LCB)

-   -   The LCB index corresponds to the branching factor g′, measured         for a molecular weight of 10⁶ g/mol. The branching factor g′,         which allows determining long-chain branches at high Mw, was         measured by Gel Permeation Chromatography (GPC) coupled with         Multi-Angle Laser-Light Scattering (MALLS), as described in the         following. The parameter g′ is the ratio of the measured mean         square radius of gyration to that of a linear polymer having the         same molecular weight. Linear molecules show g′ of 1, while         values less than 1 indicate the presence of LCB. Values of g′ as         a function of mol. weight, M, were calculated from the equation:

g′(M)=<Rg ²>_(sample,M) /<Rg ²>_(linear ref.,M)

-   -   where <Rg²>,M is the root-mean-square radius of gyration for the         fraction of mol. weight M.     -   The radius of gyration for each fraction eluted from the GPC (as         described above but with a flow-rate of 0.6 ml/min and a column         packed with 30 nm particles) is measured by analyzing the light         scattering at the different angles. Therefore, from this MALLS         setup it is possible to determine mol. weight M and         <Rg²>_(sample,M) and to define a g′ at a measured M=10⁶ g/mol.         The <Rg²>_(linear ref.,M) is calculated by the established         relation between radius-of-gyration and molecular weight for a         linear polymer in solution (Zimm and Stockmayer W H 1949)) and         confirmed by measuring a linear PE reference with the same         apparatus and methodology described.     -   The same protocol is described in the following documents.

-   Zimm B H, Stockmayer W H (1949) The dimensions of chain molecules     containing branches and rings. J Chem Phys 17

-   Rubinstein M., Colby R H. (2003), Polymer Physics, Oxford University     Press

Comonomer Content

-   -   The comonomer content is determined by means of IR in accordance         with ASTM D 6248 98, using an FT-IR spectrometer Tensor 27 from         Bruker, calibrated with a chemometric model for determining         ethyl- or butyl-side-chains in PE for butene or hexene as         comonomer, respectively.

Swell Ratio

-   -   The Swell-ratio of the studied polymers is measured utilizing a         capillary rheometer, Göttfert Rheotester2000 and Rheograph25, at         T=190° C., equipped with a commercial 30/2/2/20 die (total         length 30 mm, Active length=2 mm, diameter=2 mm, L/D=2/2 and 20°         entrance angle) and an optical device (laser-diod from Göttfert)         for measuring the extruded strand thickness. Sample is molten in         the capillary barrel at 190° C. for 6 min and extruded with a         piston velocity corresponding to a resulting shear-rate at the         die of 1440 s⁻¹. The extrudate is cut (by an automatic cutting         device from Göttfert) at a distance of 150 mm from the die-exit,         at the moment the piston reaches a position of 96 mm from the         die-inlet. The extrudate diameter is measured with the         laser-diod at a distance of 78 mm from the die-exit, as a         function of time. The maximum value corresponds to the         D_(extrudate). The swell-ratio is determined from the         calculation: SR═(D_(extrudate)−D_(die))100%/D_(die)     -   where D_(die) is the corresponding diameter at the die exit,         measured with the laser-diod.

Shrinkage@1500 s⁻¹ (Shrinkage Lab-Test)

-   -   This method is applied in order to determine the shrinkage of         the final product of polyethylene after melt-extrusion, or in         other words the dimension stability potential of a grade. The         method is recommended for homogeneous PE in granulate form.         Samples in powder can be measured, only after stabilizing and         melt-homogenization (typically in a lab-plasticizer-kneader).         However in the latter case, one should expect a significant         effect on the results, mainly due to the fact that the sample is         more sensitive to degradation and air-bubbles in the extrudate.     -   The samples in granulate form can be used directly and         approximately 20 g of sample are needed for filling the         capillary barrel. The utilized capillary rheometer is a Göttfert         Rheotester 2000, with a 15 mm diameter barrel and applicable         pressure range 0-2000 bar, temperatures 25-400° C., equipped         with a 30/2/2/20 die, with total length 30 mm, L/D=2/2 and 20°         entrance angle. The recommended test temperature for         polyethylene is 210° C.     -   The piston speed is set in order to have the required apparent         shear rate at the die exit. The test is performed at shear rates         50 s⁻¹, 1000 s⁻¹, 1500 s⁻¹ and 2500 s⁻¹.     -   The extrudate is marked and pieces of 40 mm length each are         punched/stamped, while still in the molten-state, and left to         cool at room temperature. At least 3 parts of 40 mm must be         marked in this way. A pinch-off metal-tool is utilized to stamp         the extrudate after the die-exit in the parts to be measured,         with a length of 40 mm (initial length for each part, L_(i,0))         and typically 10 mm wide.     -   The whole extrudate is cut and left on a lab table to         crystallize and cool down at room temperature for at least 15         min. The parts are cut at the marks and measured in length. The         resulting length, L_(i), in mm is recorded for each part i and         averaged for 4 parts.

${Shrinkage}_{i} = {{\frac{L_{0} - L_{i}}{L_{0}} \times 100\%} = {\frac{\Delta \; L_{i}}{L_{0}} \times 100\%}}$ ${Shrinkage}_{average} = \frac{\sum{Shinkage}_{i}}{i}$

The procedure is undertaken for each applied shear-rate and the measurement of shrinkage for each shear-rate is repeated at least two times.

Remark: Deviations of the shrinkage along the extrudate length are expected, i.e. due to varying cooling time after exiting the die for each part and sagging (the punched part leaving last the die will be less time exposed to room temperature and “stretched” due to the extrudate weight).

Critical Shear Rate for Sharkskin (Sharkskin Test)

-   -   The sharkskin test is a method to quantify the         flow-instabilities and surface defects occurring during         extrusion of polymer melts. Specifically, the commercial         sharkskin-option with the Rheotester2000 capillary rheometer         from Göttfert is used. The sharkskin-option is a slit-die of         30×3×0.3 mm with three pressure transducers distributed along         the die (at die-entry, middle and before die-exit). The pressure         is recorded and analyzed (Fourier-transformation) using the         available commercial Göttfert WebRheo software.     -   The polymer is extruded at 190° C. applying the following         shear-rates in this specific order:         100-150-200-250-300-350-400-450-500 s⁻¹. The extrudate is         consequently visually inspected for surface defects. The         critical shear-rate for sharkskin instability is the applied         shear-rate for which the sharkskin instability first occurs         (high frequency pressure oscillations and visually detectable         periodic surface distortions).

The same protocol is described in the following documents.

-   Palza H., Naue I. F. C., Wilhelm M., Filipe S., Becker A., Sunder     J., Göttfert A., On-Line Detection of Polymer Melt Flow     Instabilities in a Capillary Rheometer, KGK. Kautschuk, Gummi,     Kunststoffe, 2010, vol. 63, no 10, pp. 456-461. -   Susana Filipe, Iakovos Vittorias, Manfred Wilhelm, Experimental     Correlation between Mechanical Non-Linearity in LAOS Flow and     Capillary Flow Instabilities for Linear and Branched Commercial     Polyethylenes, Macromol. Mat. and Eng., Volume 293, Issue 1, pages     57-65, 2008. -   Göttfert, A.; Sunder, J., AIP Conference Proceedings, Volume 1027,     pp. 1195-1197 (2008).

Notched Tensile Impact Test

-   -   The tensile-impact strength is determined using ISO 8256:2004         with type 1 double notched specimens according to method A. The         test specimens (4×10×80 mm) are cut form a compression molded         sheet which has been prepared according ISO 1872-2 requirements         (average cooling rate 15 K/min and high pressure during cooling         phase). The test specimens are notched on two sides with a 45°         V-notch. Depth is 2±0.1 mm and curvature radius on notch dip is         1.0±0.05 mm. The free length between grips is 30±2 mm. Before         measurement, all test specimens are conditioned at a constant         temperature of −30° C. over a period of from 2 to 3 hours. The         procedure for measurements of tensile impact strength including         energy correction following method A is described in ISO 8256.

Environmental Stress Cracking Resistance According to Full Notch Creep Test (FNCT)

The environmental stress cracking resistance of polymer samples is determined in accordance to international standard ISO 16770 (FNCT) in aqueous surfactant solution. From the polymer sample a compression moulded 10 mm thick sheet has been prepared. The bars with squared cross section (10×10×100 mm) are notched using a razor blade on four sides perpendicularly to the stress direction. A notching device described in M. Fleissner in Kunststoffe 77 (1987), pp. 45 is used for the sharp notch with a depth of 1.6 mm. The load applied is calculated from tensile force divided by the initial ligament area. Ligament area is the remaining area=total cross-section area of specimen minus the notch area. For FNCT specimen: 10×10 mm²−4 times of trapezoid notch area=46.24 mm² (the remaining cross-section for the failure process/crack propagation). The test specimen is loaded with standard condition suggested by the ISO 16770 with constant load of 4 MPa at 80° C. in a 2% (by weight) water solution of non-ionic surfactant ARKOPAL N100. Time until rupture of test specimen is detected.

Charpy aFM

-   -   Fracture toughness determination by an internal method on test         bars measuring 10×10×80 mm which had been sawn out of a         compression molded sheet with a thickness of 10 mm. Six of these         test bars are notched in the center using a razor blade in the         notching device mentioned above for FNCT. The notch depth is         1.6 mm. The measurement is carried out substantially in         accordance with the Charpy measurement method in accordance with         ISO 179-1, with modified test specimens and modified impact         geometry (distance between supports). All test specimens are         conditioned to the measurement temperature of 0° C. over a         period of from 2 to 3 hours. A test specimen is then placed         without delay onto the support of a pendulum impact tester in         accordance with ISO 179-1. The distance between the supports is         60 mm. The drop of the 2 J hammer is triggered, with the drop         angle being set to 160°, the pendulum length to 225 mm and the         impact velocity to 2.93 m/s. The fracture toughness value is         expressed in kJ/m² and is given by the quotient of the impact         energy consumed and the initial cross-sectional area at the         notch, aFM. Only values for complete fracture and hinge fracture         can be used here as the basis for a common meaning (see         suggestion by ISO 179-1).

Examples 1, 2 and Comparative Examples 1 and 2 Process Setup

In Examples 1-2 the process of the invention was carried out under continuous conditions in a plant comprising two serially connected gas-phase reactors, as shown in FIG. 1. Comparative Example 1 is carried out in the same plant under continuous conditions as well.

Example 1

-   -   The solid catalyst component was prepared as described in         Example 13 of WO2004106388. The AcOEt/Ti molar ratio was of 8.     -   Polymerization

7 g/h of the he solid catalyst component prepared as described above were fed, using 5 kg/h of liquid propane, to a precontacting apparatus, in which also a mixture of triisobuthylaluminum (TIBA) and diethylaluminum chloride (DEAC) as well tetrahydrofuran (THF) were dosed. The weight ratio between TIBA and DEAC was 7:1. The weight ratio between aluminum alkyl and solid catalyst component was 10:1. The weight ratio between aluminum alkyl and THF was 70. The precontacting step was carried out under stirring at 50° C. with a total residence time of 70 minutes.

The catalyst enters the first gas-phase polymerization reactor 1 of FIG. 1 via line 10. In the first reactor ethylene was polymerized using H₂ as molecular weight regulator and in the presence of propane as inert diluent. 35 kg/h of ethylene and 62 g/h of hydrogen were fed to the first reactor via line 9. No comonomer was fed to the first reactor.

The polymerization was carried out at a temperature of 75° C. and at a pressure of 2.5 MPa. The polymer obtained in the first reactor was discontinuously discharged via line 11, separated from the gas into the gas/solid separator 12, and reintroduced into the second gas-phase reactor via line 14.

The polymer produced in the first reactor had a melt index MIE of about 25 g/10 min and a density of 0.966 kg/dm³.

The second reactor was operated under polymerization conditions of about 80° C., and a pressure of 2.5 MPa. 14 kg/h of ethylene and 0.75 kg/h of 1-hexene were introduced in the downcomer 33 of the second reactor via line 46. 5 kg/h of propane, 28.5 kg/h of ethylene and 3.1 g/h of hydrogen were fed through line 45 into the recycling system.

In order to broaden the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of monomers and hydrogen concentration within the riser 32 and the downcomer 33. This is achieved by feeding via line 52, 330 kg/h of a liquid stream (liquid barrier) into the upper part of the downcomer 33. Said liquid stream has a composition different from that of the gas mixture present in the riser. Said different concentrations of monomers and hydrogen within the riser, the downcomer of the second reactor and the composition of the liquid barrier are indicated in Table 1. The liquid stream of line 52 comes from the condensation step in the condenser 49, at working conditions of 52° C. and 2.5 MPa, wherein a part of the recycle stream is cooled and partially condensed. As shown in the FIGURE, a separating vessel and a pump are placed, in the order, downstream the condenser 49. The final polymer was discontinuously discharged via line 54.

The polymerization process in the second reactor produced relatively high molecular weight polyethylene fractions. In Table 1 the properties of the final product are specified. It can be to seen that the melt index of the final product is decreased as compared to the ethylene resin produced in the first reactor, showing the formation of high molecular weight fractions in the second reactor.

The first reactor produced around 44.5% by weight (split wt %) of the total amount of the final polyethylene resin produced by both first and second reactors. At the same time, the obtained polymer is endowed with a relatively broad molecular weight distribution as witnessed by a ratio MIF/MIP equal to 23.7.

Example 2

The process of the invention was carried out with the same setup and the same polymerization catalyst of Example 1. Also the process conditions and consequently the obtained polymer properties of the first reactor were the same.

The second reactor was operated under polymerization conditions of about 80° C., and a pressure of 2.5 MPa. 14 kg/h of ethylene and 0.86 kg/h of 1-hexene were introduced in the downcomer of the second reactor via line 46. 5 kg/h of propane, 27.4 kg/h of ethylene and 3.6 g/h of hydrogen were fed through line 45 into the recycling system.

In order to broaden again the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of monomers and hydrogen concentration within the riser 32 and the downcomer 33. Again 330 kg/h of barrier liquid were fed via line 52. The gas compositions of the riser, the downcomer and the liquid barrier are indicated in Table 1. The liquid stream of line 52 comes from the condensation step in the condenser 49, at working conditions of 51° C. and 2.5 MPa, wherein a part of the recycle stream is cooled and partially condensed.

The first reactor produced around 45% by weight (split wt %) of the total amount of the final polyethylene resin produced by both first and second reactors. At the same time, the obtained polymer is endowed with a relatively broad molecular weight distribution as witnessed by a ratio MIF/MIP equal to 22.5.

Comparative Example 1

The polymerization was carried out using the same setup of Examples 1 and 2, but the polymerization catalyst was the same as used in example 6 of WO2005019280.

8 g/h of the solid catalyst component prepared as described above were fed, using 5 kg/h of liquid propane, to a precontacting apparatus, in which triethylaluminum (TEA) as well tetrahydrofuran (THF) were dosed. The weight ratio between aluminum alkyl and solid catalyst component was 5:1. The weight ratio between aluminum alkyl and THF was 44. The precontacting step was carried out under stirring at 50° C. with a total residence time of 70 minutes.

The catalyst enters the first gas-phase polymerization reactor 1 of FIG. 1 via line 10. In the first reactor ethylene was polymerized using H₂ as molecular weight regulator and in the presence of propane as inert diluent. 40 kg/h of ethylene and 75 g/h of hydrogen were fed to the first reactor via line 9. No comonomer was fed to the first reactor.

The polymerization was carried out at a temperature of 80° C. and at a pressure of 2.4 MPa. The polymer obtained in the first reactor was discontinuously discharged via line 11, separated from the gas into the gas/solid separator 12, and reintroduced into the second gas-phase reactor via line 14.

The polymer produced in the first reactor had a melt index MIE of about 100 g/10 min and a density of 0.968 kg/dm³.

The second reactor was operated under polymerization conditions of about 80° C., and a pressure of 2.1 MPa. 12 kg/h of ethylene and 1.5 kg/h of 1-hexene were introduced in the downcomer 33 of the second reactor via line 46. 5 kg/h of propane, 26.5 kg/h of ethylene and 1.2 g/h of hydrogen were fed through line 45 into the recycling system.

In order to broaden the molecular weight distribution of the final ethylene polymer, the second reactor was operated by establishing different conditions of monomers and hydrogen concentration within the riser 32 and the downcomer 33. This is achieved by feeding via line 52, 200 kg/h of a liquid stream (liquid barrier) into the upper part of the downcomer 33. Said liquid stream has a composition different from that of the gas mixture present in the riser. Said different concentrations of monomers and hydrogen within the riser, the downcomer of the second reactor and the composition of the liquid barrier are indicated in Table 1. The liquid stream of line 52 comes from the condensation step in the condenser 49, at working conditions of 53° C. and 2.1 MPa, wherein a part of the recycle stream is cooled and partially condensed. As shown in the FIGURE, a separating vessel and a pump are placed, in the order, downstream the condenser 49. The final polymer was discontinuously discharged via line 54.

The polymerization process in the second reactor produced relatively high molecular weight polyethylene fractions. In Table 1 the properties of the final product are specified. It can be seen that the melt index of the final product is decreased as compared to the ethylene resin produced in the first reactor, showing the formation of high molecular weight fractions in the second reactor.

The first reactor produced around 50% by weight (split wt %) of the total amount of the final polyethylene resin produced by both first and second reactors. At the same time, the obtained polymer is endowed with a relatively broad molecular weight distribution as witnessed by a ratio MIF/MIP equal to 38.8

Comparative Example 2

The polymer of this comparative example is a prior-art polyethylene composition prepared with a Cr-catalyst, in a single gas-phase reactor.

TABLE 1 Ex. 1 Ex. 2 Comp. 1 Comp. 2 Operative conditions first reactor H₂/C₂H₄ Molar ratio 1.9 1.9 1.7 C₂H₄% 12.1 12.4 14 Split (wt %) 44.5 45 50 Operative conditions second reactor H₂/C₂H₄ Molar ratio riser 0.157 0.203 0.038 C₂H₄% riser 11.3 11.4 15 C₆H₁₂ riser 0.56 0.65 1.2 H₂/C₂H₄ Molar ratio downcomer 0.069 0.086 0.04 C₂H₄% downcomer 2.6 2.8 5.4 C₆H₁₂ downcomer 0.60 0.71 2.2 H₂/C₂H₄ Molar ratio barrier 0.013 0.015 0.01 C₂H₄% barrier 6.8 7.1 6.5 C₆H₁₂ barrier 0.93 1.17 2.7 Final Polymer properties MIP [5 kg] (g/10 min.) 0.2 0.29 0.21 0.31 MIF [21.6 kg] (g/10 min.) 4.8 6.5 8.15 6.25 MIF/MIP 23.7 22.5 38.8 20.16 Density (kg/dm³) 0.9509 0.9496 0.9487 0.947 Mw [g/mol] 3.5E+5 3.8E+5 3.6E+5 3.9E+5 Mz [g/mol] 2.0E+6 8.3E+6 5.0E+6 3.5E+6 Mw/Mn 25 27 52 25 LCB 0.89 0.84 0.69 0.99 Comonomer content IR 0.7% ± 0.1 0.7% ± 0.1 1.6 1.6 [% by weight] (C₆H₁₂) (C₆H₁₂) (C₆H₁₂) (C₆H₁₂) SIC index 3.8 3.3 1.9 6.1 Swell ratio (%) 179 171 120 210 Shrinkage@1500 s⁻¹, 15 12 — 23 T = 190° C. [%] Critical shear-rate for sharkskin, 300 300 — 200 T = 190° C., [1/s] Notched-Tensile Impact test, 164 155 93 145 T = −30° C. [kJ/m²] FNCT 4 MPa/80° C. (hours)* 329 20 >2000 4 Charpy aFM, T = 0° C. [kJ/m²] — — 8.9 Notes: C₂H₄ = ethylene; C₆H₁₂ = hexene; *aqueous solution of 2% Arkopal N100 

1. A polyethylene composition having the following properties: 1) a density from 0.945 to less than 0.952 g/cm³, determined according to ISO 1183 at 23° C.; 2) a ratio MIF/MIP from 15 to 30, wherein the MIF is the melt flow index at 190° C. with a load of 21.60 kg, and the MIP is the melt flow index at 190° C. with a load of 5 kg, both determined according to ISO 1133; 3) a SIC Index from 2.5 to 5.5; wherein the SIC Index is the Shear-Induced Crystallization Index, determined according to the following relation: SIC Index=(t _(onset,SIC)@1000×t _(onset,quiescent))/(HLMI) where t_(onset,SIC)@1000 is measured in seconds and is the time required for crystallization onset under shear rate of 1000 s⁻¹, the t_(onset, quiescent) is measured in seconds and is the crystallization onset time at temperature of 125° C. under no shear, determined in isothermal mode by differential scanning calorimetry; HLMI is the melt flow index determined at 190° C. with a load of 21.6 kg, according to ISO
 1133. 2. The polyethylene composition of claim 1, comprising one or more ethylene copolymers.
 3. The polyethylene composition of claim 2, wherein the one or more ethylene copolymers have a comonomer content equal to or less than 1% by weight.
 4. The polyethylene composition of claim 2, wherein the comonomer is selected from olefins having formula CH₂═CHR wherein R is an alkyl radical, linear or branched, having from 1 to 10 carbon atoms.
 5. The polyethylene composition of claim 1, obtainable by using a Ziegler-Natta polymerization catalyst.
 6. The polyethylene composition of claim 1, having at least one of the following properties: a Mw equal to or greater than 250000 g/mol; a Mw/Mn from 20 to 30; a Long Chain Branching index equal to or greater than 0.70, in particular equal to or greater than 0.72; a MIP from 0.05-0.5 g/10 min.; a MIF from 1-15 g/10 min.
 7. The polyethylene composition of claim 1, comprising: A) 30-50% by weight of an ethylene homopolymer or copolymer with density equal to or greater than 0.960 g/cm³ and melt flow index MIE at 190° C. with a load of 2.16 kg, according to ISO 1133, of 10-35 g/10 min.; B) 50-70% by weight of an ethylene copolymer having a MIE value lower than the MIE value of A).
 8. A manufactured article comprising the polyethylene composition of claim
 1. 9. A manufactured article according to claim 8, in form of a blow-moulded article.
 10. The polyethylene composition of claim 1, wherein the polyethylene composition is formed in one or more polymerizing steps, wherein all the polymerization steps are carried out in the presence of a Ziegler-Natta polymerization catalyst supported on MgCl₂.
 11. The polyethylene composition of claim 10, wherein the one or more polymerizing steps comprise the following steps, in any mutual order: a) polymerizing ethylene, optionally together with one or more comonomers, in a gas-phase reactor in the presence of hydrogen; b) copolymerizing ethylene with one or more comonomers in another gas-phase reactor in the presence of an amount of hydrogen less than step a); where in at least one of said gas-phase reactors the growing polymer particles flow upward through a first polymerization zone under fast fluidization or transport conditions, leave said riser and enter a second polymerization zone through which they flow downward under the action of gravity, leave said second polymerization zone and are reintroduced into the first polymerization zone, thus establishing a circulation of polymer between said two polymerization zones. 